A 2D ferroelectric vortex pattern in twisted BaTiO3 freestanding layers.

The wealth of complex polar topologies1-10 recently found in nanoscale ferroelectrics results from a delicate balance between the intrinsic tendency of the materials to develop a homogeneous polarization and the electric and mechanical boundary conditions imposed on them. Ferroelectric-dielectric interfaces are model systems in which polarization curling originates from open circuit-like electric boundary conditions, to avoid the build-up of polarization charges through the formation of flux-closure11-14 domains that evolve into vortex-like structures at the nanoscale15-17 level. Although ferroelectricity is known to couple strongly with strain (both homogeneous18 and inhomogeneous19,20), the effect of mechanical constraints21 on thin-film nanoscale ferroelectrics has been comparatively less explored because of the relative paucity of strain patterns that can be implemented experimentally. Here we show that the stacking of freestanding ferroelectric perovskite layers with controlled twist angles provides an opportunity to tailor these topological nanostructures in a way determined by the lateral strain modulation associated with the twisting. Furthermore, we find that a peculiar pattern of polarization vortices and antivortices emerges from the flexoelectric coupling of polarization to strain gradients. This finding provides opportunities to create two-dimensional high-density vortex crystals that would enable us to explore previously unknown physical effects and functionalities.

Large intrinsic anomalous Hall effect in SrIrO3 induced by magnetic proximity effect.

The anomalous Hall effect (AHE) is an intriguing transport phenomenon occurring typically in ferromagnets as a consequence of broken time reversal symmetry and spin-orbit interaction. It can be caused by two microscopically distinct mechanisms, namely, by skew or side-jump scattering due to chiral features of the disorder scattering, or by an intrinsic contribution directly linked to the topological properties of the Bloch states. Here we show that the AHE can be artificially engineered in materials in which it is originally absent by combining the effects of symmetry breaking, spin orbit interaction and proximity-induced magnetism. In particular, we find a strikingly large AHE that emerges at the interface between a ferromagnetic manganite (La0.7Sr0.3MnO3) and a semimetallic iridate (SrIrO3). It is intrinsic and originates in the proximity-induced magnetism present in the narrow bands of strong spin-orbit coupling material SrIrO3, which yields values of anomalous Hall conductivity and Hall angle as high as those observed in bulk transition-metal ferromagnets. These results demonstrate the interplay between correlated electron physics and topological phenomena at interfaces between 3d ferromagnets and strong spin-orbit coupling 5d oxides and trace an exciting path towards future topological spintronics at oxide interfaces.

Controlled Sign Reversal of Electroresistance in Oxide Tunnel Junctions by Electrochemical-Ferroelectric Coupling.

The persistence of ferroelectricity in ultrathin layers relies critically on screening or compensation of polarization charges which otherwise destabilize the ferroelectric state. At surfaces, charged defects play a crucial role in the screening mechanism triggering novel mixed electrochemical-ferroelectric states. At interfaces, however, the coupling between ferroelectric and electrochemical states has remained unexplored. Here, we make use of the dynamic formation of the oxygen vacancy profile in the nanometer-thick barrier of a ferroelectric tunnel junction to demonstrate the interplay between electrochemical and ferroelectric degrees of freedom at an oxide interface. We fabricate ferroelectric tunnel junctions with a La_{0.7}Sr_{0.3}MnO_{3} bottom electrode and BaTiO_{3} ferroelectric barrier. We use poling strategies to promote the generation and transport of oxygen vacancies at the metallic top electrode. Generated oxygen vacancies control the stability of the ferroelectric polarization and modify its coercive fields. The ferroelectric polarization, in turn, controls the ionization of oxygen vacancies well above the limits of thermodynamic equilibrium, triggering the build up of a Schottky barrier at the interface which can be turned on and off with ferroelectric switching. This interplay between electronic and electrochemical degrees of freedom yields very large values of the electroresistance (more than 10^{6}% at low temperatures) and enables a controlled switching between clockwise and counterclockwise switching modes in the same junction (and consequently, a change of the sign of the electroresistance). The strong coupling found between electrochemical and electronic degrees of freedom sheds light on the growing debate between resistive and ferroelectric switching in ferroelectric tunnel junctions, and moreover, can be the source of novel concepts in memory devices and neuromorphic computing.

A new method to detect and correct sample tilt in scanning transmission electron microscopy bright-field imaging.

Important properties of functional materials, such as ferroelectric shifts and octahedral distortions, are associated with displacements of the positions of lighter atoms in the unit cell. Annular bright-field scanning transmission electron microscopy is a good experimental method for investigating such phenomena due to its ability to image light and heavy atoms simultaneously. To map atomic positions at the required accuracy precise angular alignment of the sample with the microscope optical axis is necessary, since misalignment (tilt) of the specimen contributes to errors in position measurements of lighter elements in annular bright-field imaging. In this paper it is shown that it is possible to detect tilt with the aid of images recorded using a central bright-field detector placed within the inner radius of the annular bright-field detector. For a probe focus near the middle of the specimen the central bright-field image becomes especially sensitive to tilt and we demonstrate experimentally that misalignment can be detected with a precision of less than a milliradian, as we also confirm in simulation. Coma in the probe, an aberration that can be misidentified as tilt of the specimen, is also investigated and it is shown how the effects of coma and tilt can be differentiated. The effects of tilt may be offset to a large extent by shifting the diffraction plane detector an amount equivalent to the specimen tilt and we provide an experimental proof of principle of this using a segmented detector system.

Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces.

At interfaces between conventional materials, band bending and alignment are classically controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from strong Coulomb interactions between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence.

Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces.

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.

Formation of titanium monoxide (001) single-crystalline thin film induced by ion bombardment of titanium dioxide (110).

A plethora of technological applications justify why titanium dioxide is probably the most studied oxide, and an optimal exploitation of its properties quite frequently requires a controlled modification of the surface. Low-energy ion bombardment is one of the most extended techniques for this purpose and has been recently used in titanium oxides, among other applications, to favour resistive switching mechanisms or to form transparent conductive layers. Surfaces modified in this way are frequently described as reduced and defective, with a high density of oxygen vacancies. Here we show, at variance with this view, that high ion doses on rutile titanium dioxide (110) induce its transformation into a nanometric and single-crystalline titanium monoxide (001) thin film with rocksalt structure. The discovery of this ability may pave the way to new technical applications of ion bombardment not previously reported, which can be used to fabricate heterostructures and interfaces.

Reversible electric-field control of magnetization at oxide interfaces.

Electric-field control of magnetism has remained a major challenge which would greatly impact data storage technology. Although progress in this direction has been recently achieved, reversible magnetization switching by an electric field requires the assistance of a bias magnetic field. Here we take advantage of the novel electronic phenomena emerging at interfaces between correlated oxides and demonstrate reversible, voltage-driven magnetization switching without magnetic field. Sandwiching a non-superconducting cuprate between two manganese oxide layers, we find a novel form of magnetoelectric coupling arising from the orbital reconstruction at the interface between interfacial Mn spins and localized states in the CuO2 planes. This results in a ferromagnetic coupling between the manganite layers that can be controlled by a voltage. Consequently, magnetic tunnel junctions can be electrically toggled between two magnetization states, and the corresponding spin-dependent resistance states, in the absence of a magnetic field.

Characterization of surface metallic states in SrTiO3 by means of aberration corrected electron microscopy.

An unusual conducting surface state can be produced in SrTiO3 substrates by irradiation with Argon ions from a plasma source, at low energy and high doses. The effects of irradiation are analyzed here by atomic force microscopy (AFM) and aberration corrected scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS). Depth sensitive studies demonstrate the existence of a heavily damaged surface layer and an oxygen vacancy rich layer immediately underneath, both induced during the irradiation process. We find a clear dependence of the Ti oxidation state with the depth, with a very intense Ti(3+) component near the surface. Oxygen vacancies act as n-type doping by releasing electrons into the lattice and producing an insulator-to-metal transition, which explains the unusual metallic behavior of these samples.